EP0328333A2 - Procédé pour la fabrication de céramiques supraconductrices - Google Patents
Procédé pour la fabrication de céramiques supraconductrices Download PDFInfo
- Publication number
- EP0328333A2 EP0328333A2 EP89301140A EP89301140A EP0328333A2 EP 0328333 A2 EP0328333 A2 EP 0328333A2 EP 89301140 A EP89301140 A EP 89301140A EP 89301140 A EP89301140 A EP 89301140A EP 0328333 A2 EP0328333 A2 EP 0328333A2
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- European Patent Office
- Prior art keywords
- process according
- barium
- substrate
- chelate
- strontium
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000919 ceramic Substances 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000002887 superconductor Substances 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052788 barium Inorganic materials 0.000 claims abstract description 27
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 26
- 239000000470 constituent Substances 0.000 claims abstract description 14
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 7
- 230000008016 vaporization Effects 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims description 24
- 239000013522 chelant Substances 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 20
- 229910052727 yttrium Inorganic materials 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 13
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- QISKERKMOGSCJB-UHFFFAOYSA-N 4-iminopentan-2-one Chemical compound CC(=N)CC(C)=O QISKERKMOGSCJB-UHFFFAOYSA-N 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000032258 transport Effects 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- GRTBAGCGDOYUBE-UHFFFAOYSA-N yttrium(3+) Chemical compound [Y+3] GRTBAGCGDOYUBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 238000000151 deposition Methods 0.000 abstract description 12
- 238000009834 vaporization Methods 0.000 abstract description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract 2
- 238000005019 vapor deposition process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 35
- 150000001875 compounds Chemical class 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000008021 deposition Effects 0.000 description 10
- 238000004544 sputter deposition Methods 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- -1 alkaline earth metal carbonate Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910002264 La1.85Sr0.15CuO4 Inorganic materials 0.000 description 2
- MGYPLPRYNYINRY-UHFFFAOYSA-N [Cu]=O.[Sr].[La] Chemical compound [Cu]=O.[Sr].[La] MGYPLPRYNYINRY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- FFWQPZCNBYQCBT-UHFFFAOYSA-N barium;oxocopper Chemical class [Ba].[Cu]=O FFWQPZCNBYQCBT-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002282 La2CuO4 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910001275 Niobium-titanium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- KFVPJMZRRXCXAO-UHFFFAOYSA-N [He].[O] Chemical compound [He].[O] KFVPJMZRRXCXAO-UHFFFAOYSA-N 0.000 description 1
- CNEWPRQQHICZBP-UHFFFAOYSA-N [O].[Cu].[Ba].[La] Chemical compound [O].[Cu].[Ba].[La] CNEWPRQQHICZBP-UHFFFAOYSA-N 0.000 description 1
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DJHZYHWLGNJISM-FDGPNNRMSA-L barium(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ba+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O DJHZYHWLGNJISM-FDGPNNRMSA-L 0.000 description 1
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical compound [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- YYMDQTCBBBXDRH-UHFFFAOYSA-N lanthanum;oxocopper Chemical compound [La].[Cu]=O YYMDQTCBBBXDRH-UHFFFAOYSA-N 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KJSMVPYGGLPWOE-UHFFFAOYSA-N niobium tin Chemical compound [Nb].[Sn] KJSMVPYGGLPWOE-UHFFFAOYSA-N 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 229910000657 niobium-tin Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011364 vaporized material Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
- H10N60/0436—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD]
- H10N60/0464—Processes for depositing or forming copper oxide superconductor layers by chemical vapour deposition [CVD] by metalloorganic chemical vapour deposition [MOCVD]
Definitions
- This invention relates to a process for producing ceramic superconductors continuing barium and/or strontium.
- the recent discovery by Muller and Bednorz of ceramic superconductors which are superconductive at relatively high temperatures has dramatically increased the interest in superconductivity and resulted in a large number of publications.
- the previous metallic superconductors such as niobium-tin or niobium-titanium required expensive liquid helium cooling.
- the new ceramic superconductors can be cooled by a relatively inexpensive means, such as liquid nitrogen.
- the ceramic superconductors have generally been oxides of at least one rare earth (hereafter the term "rare earth” will be understood to include yttrium as well as the lanthanide elements, unless otherwise stated), at least one alkaline earth metal, and copper.
- the superconductors have been prepared by milling oxides of the rare earth and copper with an alkaline earth metal carbonate (e.g. yttrium oxide, copper oxide, and barium carbonate) and firing the mixture in an oxidizing atmospher at 1000-1100C, (typically regrinding, refiring, etc. a number of times) and then annealing the ceramic in an oxygen atmosphere at 400-900C for an extended period of time (e.g. 0.5-5 days).
- an alkaline earth metal carbonate e.g. yttrium oxide, copper oxide, and barium carbonate
- Yoshizaki et al. in a paper entitled "Superconducting Properties of La 1.85 Sr 0.15 CuO4 Made by Hot Press and Sintered Methods” investigated superconducting transition properties by resistivity and magnetization in lanthanum-strontium-copper oxide for hot pressed and sintered samples. A single crystal was obtained in a portion of one sample.
- U.S. Patent Specification Nos. 4,411,959 and 4,575,927 (Braginski et al.), issued October 25, 1983 and march 18, 1986, respectively, teach a submicron particle superconductor arrangement in which brittle superconductive particles remain unsintered in the fabricated wire, thus give a ductile wire, even though the superconducting material is brittle.
- the small particles provide spacing between particles of much less than the Ginzburg-Landau coherence lengths to avoid any significant degradation to T c .
- U.S. Patent Specification No. 4,419,125 (Charles et al.) teaches using liquid alkali metal to co-reduce a mixture of solid halides to produce such submicron powders.
- the present invention resides in a process for procuding ceramic superconductors containing barium and/or strontium characterized by vaporizing chelates of metallic constituents of the superconductor at 150-135C, thereby producing a chelate composite vapor; mixing said chelate composite vapor with oxygen-containing gas to produce a gaseous chemical vapor deposition mixture; heating a substrate to from 350 to 650C; and contacting said gaseous chemical vapor deposition mixture to said substrate to produce a ceramic film.
- the substrate is a single crystal perovskite (e.g. strontium titanate) substrate.
- the metallic constituents are yttrium, copper and barium and/or strontium.
- Volatile chelates of these metallic constitutents are vaporized in a stream of inert carrier gas which transports the chelates to a heated substrate, the temperature of which can differ from those necessary to vaporize the chelates.
- the volatilized chelate vapors are mixed with oxygen gas (or an oxygen water-vapor mixture) to effect oxide formation at the hot substrate target.
- barium is one of the metallic constituents
- Bis [1,1,1,2,2,3,3,-heptafluoro-7,7-dimethyl-4,6-octanedionato] barium(II) is used as the barium chelate
- yttrium is one of the metallic constituents
- Tris [1,1,1,2,2,3,3,-heptafluoro-7,7-dimethyl-4,6-octanedionato] yttrium(III) is used as the yttrium chelate
- copper is one of the metallic constituents
- Bis [acetyl-acetoneimide] copper(II) is used as the copper chelate.
- strontium is one of the metallic constituents Bis [1,1,1,2,2,3,3,-heptafluoro-7,7-dimethyl-4,6-octanedionato] strontium(II) is used preferivelyably as the strontium chelate.
- films Prior to the post-baking, films may be heated to 850-950C to provide a tetragonal form and then slow cooled to allow a tetragonal to orthohombic transformation at about 650C.
- the orthohombic-pervoskite form is formed during deposition and the transformation avoided.
- Chemical vapor deposition should overcome the major deficiencies listed above.
- CVD with metal-organic (MO) source materials is widely used to prepare high quality films of GaAs and AlGaAs for microwave device and laser applications.
- MO metal-organic
- CVD is used in the preparation of films of silicon dioxide and silicon nitride which are used for insulating or masking purposes in both Si and GaAs devices and integrated circuits.
- CVD equipment for high throughput of large area semiconductor substrates exists and is undergoing continual upgrading.
- metal chelate compounds would constitute a better approach for obtaining volatile precursors of all three metals: Ba, Y, and Cu. It has been found that incorporating a multiplicity of bulky organic groups into the organic portion of such chelates tends to increase volatility of the metal chelates, often dramatically. This is due to the relatively large forces of attraction which exist between the adjacent chelate molecules in the solid or liquid form as a result of the ionic character of the metal-ligand bonds. Barium chelates have especially high intermolecular attractions due to the high ionic character of barium-ligand bonds.
- Intermolecular forces of this type are minimized by the incorporation of the bulky groups mentioned above, since metal-metal distances between adjacent molecules can be greatly increased and intermolecular forces correspondingly decreased.
- Appropriate bulky substituents which can be incorporated into metal chelates include fluorine and/or methyl groups.
- FIG. 1A shows chemical vapor deposition apparatus 10, which utilizes a resistance heated furnace 12 generally around a quartz reaction tube 14. Longitudinal distances from center lines are shown on both sides of the center line and correspond to the temperature profile as a function of longitudinal distance from center line shown in Figure 1B.
- One or more source boats 16 containing source material 18 provide material for vaporization, which vaporized material is swept downstream by helium carrier gas introduced at helium carrier gas inlet 20 and oxygen containing gas (here an oxygen helium mixture 22) is fed through oxygen feed tube 24 such that it can be mixed adjacent to (i.e. immediately before impinging) heated substrates 26.
- Auxiliary heating tape 28 was utilized to provide adjustment of the temperature of source boat 16. Gases are exhausted downstream from the substrates 26, through exhaust port 30.
- Auger analyses were made of these films.
- One example of multiple Auger profiles for a film sample deposited at about 400C is shown in Figure 2.
- the Y and O signals fell slowly by 26 to 29%, while the Ba signal increased by a factor of about 3, appearing to roughly co-vary with the copper signal, which fell by a factor of about 1/2.
- the form of the Cu profile suggests that the Cu MO source was depleted sooner than the other sources in this experiment, as there were limited amounts of each material and the volatility of the Cu(II) acetyl-acetoneimide was higher.
- the increasing barium profile toward the center of the deposited film indicates that growth of the multi-component portion of the film was not limited by barium availability.
- chelate source compounds such as Ba(hfod)2 - Bis[1,1,1,2,2,3,3,-heptafluoro-7,7-dimethyl-4,6-octanedionato] barium(II) and Y(hfod)3 - [1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl 4,6-octanedionato]yttrium(III) both of which have adequate volatility for supplying barium and yttrium in a CVD reactant stream.
- These two compounds can be used as source materials at about 300C in a CVD reactor; together with, for example, Cu(acacimide)2.
- the solid source materials can be held in individual containers and heated at temperatures below 300C to provide, with adjustable flow rates of appropriate inert carrier gases - such as helium, argon, or nitrogen - controlled concentrations of Ba-, Y-, and Cu-containing species in a CVD reactant stream and thus deposit films with selected composition.
- appropriate inert carrier gases - such as helium, argon, or nitrogen - controlled concentrations of Ba-, Y-, and Cu-containing species in a CVD reactant stream and thus deposit films with selected composition.
- Metal chelates constitute a sub-division of metal-organic compounds in which the bonded metal is part of one or more ring structures within the metal-organic molecule. Metal chelates, rather than metal-organic without ring structures, are desirable in the present application because of their enhanced heat stabilities in inert atmospheres, volatilities, and their high resistance to hydrolysis in moist air at room temperature.
- Carbon and fluorine are also supplied by the Ba and Y MO source materials and were detected in the films produced initially. It should be noted, however, that the presence of fluorine is not necessarily a detriment since some workers have recently claimed enhanced properties for the 1:2:3 compound when some of the oxygen is replaced by fluorine. However, the presence of fluorine in the deposit can be eliminated completely by substituting bulky Ba and Y chelate which do not contain fluorine. Chelates of this type are known. Examples are:
- a higher percentage of oxygen in the transport gas stream may well be sufficient to reduce carbon to acceptable levels. It is possible that a mixture of oxygen and water vapor may be even more effective.
- the novel design of equipment should be noted in which the chelates are vaporized from a multicompartmented cell (or three separate cells) and swept downstream with an inert gas to prevent premature decomposition or oxide formation.
- the metal chelate vapors then encounter a separately introduced stream of oxygen gas adjacent to (i.e. immediately before impinging) a heated quartz substitute.
- such superconducting ceramics can be post baked in an oxygen atmosphere, generally at temperatures of 400-650C.
- fluorine can be partially substituted for oxygen in such ceramics and such chelates can be used as at least one of the sources of fluorine.
- the ceramic superconductor film can be made directly, using relatively high oxygen in the gaseous chemical vapor deposition mixture and 350-650C substrate temperatures, or indirectly, using either leaner oxygen or lower substrate temperature (e.g. 150-350C) or both.
- the indirectly produced ceramic films use heating to greater than 350C to convert the polymer-containing film to an essentially polymer-free crystalline film.
- this invention describes chelate-type metal-organic materials which are volatile at 200 to 350C, as sources of Ba and/or Sr, with, for example, Y, and Cu for the chemical vapor deposition of oxide films which upon further heat treatment can yield superconducting oxide (e.g. YBa2Cu3O7).
- superconducting oxide e.g. YBa2Cu3O7.
- the multiplicity of bulky organic groups overcomes the volatility-supressing influence of the strong Ba-Ba ionic bond.
- Similar considerations apply for the Y(hfod)3 source material. Used in the simultaneous combination with Cu(II)acetyl-acetoneimide, these sources have yielded oxide films in a CVD reactor provided with a zone of appropriate deposition temperatures.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US15439388A | 1988-02-10 | 1988-02-10 | |
US154393 | 1988-02-10 |
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Publication Number | Publication Date |
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EP0328333A2 true EP0328333A2 (fr) | 1989-08-16 |
EP0328333A3 EP0328333A3 (fr) | 1990-12-27 |
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Application Number | Title | Priority Date | Filing Date |
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EP19890301140 Withdrawn EP0328333A3 (fr) | 1988-02-10 | 1989-02-06 | Procédé pour la fabrication de céramiques supraconductrices |
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EP (1) | EP0328333A3 (fr) |
JP (1) | JPH01252779A (fr) |
CA (1) | CA1338202C (fr) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0329103A2 (fr) * | 1988-02-17 | 1989-08-23 | Kabushiki Kaisha Riken | Procédé pour la fabrication de couches minces d'oxyde supraconducteur à haute température critique |
US5204314A (en) | 1990-07-06 | 1993-04-20 | Advanced Technology Materials, Inc. | Method for delivering an involatile reagent in vapor form to a CVD reactor |
US5225561A (en) * | 1990-07-06 | 1993-07-06 | Advanced Technology Materials, Inc. | Source reagent compounds for MOCVD of refractory films containing group IIA elements |
US5280012A (en) * | 1990-07-06 | 1994-01-18 | Advanced Technology Materials Inc. | Method of forming a superconducting oxide layer by MOCVD |
US5284824A (en) * | 1988-03-16 | 1994-02-08 | Kabushiki Kaisha Toshiba | Method for manufacturing an oxide superconductor thin film |
US5453494A (en) * | 1990-07-06 | 1995-09-26 | Advanced Technology Materials, Inc. | Metal complex source reagents for MOCVD |
US5711816A (en) * | 1990-07-06 | 1998-01-27 | Advanced Technolgy Materials, Inc. | Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same |
US5719417A (en) * | 1996-11-27 | 1998-02-17 | Advanced Technology Materials, Inc. | Ferroelectric integrated circuit structure |
US5876503A (en) * | 1996-11-27 | 1999-03-02 | Advanced Technology Materials, Inc. | Multiple vaporizer reagent supply system for chemical vapor deposition utilizing dissimilar precursor compositions |
US5882416A (en) * | 1997-06-19 | 1999-03-16 | Advanced Technology Materials, Inc. | Liquid delivery system, heater apparatus for liquid delivery system, and vaporizer |
US5923970A (en) * | 1997-11-20 | 1999-07-13 | Advanced Technology Materials, Inc. | Method of fabricating a ferrolelectric capacitor with a graded barrier layer structure |
US6126996A (en) * | 1990-07-06 | 2000-10-03 | Advanced Technology Materials, Inc. | Metal complex source reagents for chemical vapor deposition |
US6284654B1 (en) | 1998-04-16 | 2001-09-04 | Advanced Technology Materials, Inc. | Chemical vapor deposition process for fabrication of hybrid electrodes |
WO2003044242A2 (fr) * | 2001-11-16 | 2003-05-30 | Applied Materials, Inc. | Depot de couche atomique de cuivre au moyen d'un gaz de reduction et de precurseurs de cuivre non fluores |
EP1564489A1 (fr) | 2004-02-10 | 2005-08-17 | General Electric Company | Bougie d'allumage de chambre de combustion de turbine à gaz |
EP1655788A2 (fr) * | 2004-11-03 | 2006-05-10 | Nexans | Précurseur pour supraconducteurs à base de YBCO |
EP1655787A1 (fr) * | 2004-11-03 | 2006-05-10 | Nexans | Composition de précurseur pour supraconducteur à base de YBCO |
US8299286B2 (en) | 1990-07-06 | 2012-10-30 | Advanced Technology Materials, Inc. | Source reagent compositions and method for forming metal films on a substrate by chemical vapor deposition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01208323A (ja) * | 1988-02-17 | 1989-08-22 | Riken Corp | 薄膜製造法 |
JPH0829943B2 (ja) * | 1988-05-13 | 1996-03-27 | 沖電気工業株式会社 | 超伝導体薄膜の形成方法 |
US5458086A (en) * | 1993-10-13 | 1995-10-17 | Superconductor Technologies, Inc. | Apparatus for growing metal oxides using organometallic vapor phase epitaxy |
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US3594216A (en) * | 1969-06-19 | 1971-07-20 | Westinghouse Electric Corp | Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate |
EP0125638A2 (fr) * | 1983-05-13 | 1984-11-21 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Film précurseur pour film céramique, son utilisation et son procédé de préparation |
US4485094A (en) * | 1983-01-28 | 1984-11-27 | Westinghouse Electric Corp. | Method of making ABO3 of the cubic perovskite structure |
DE3827069A1 (de) * | 1987-11-21 | 1989-06-08 | Asea Brown Boveri | Verfahren zur herstellung eines supraleiters |
-
1989
- 1989-01-30 CA CA000589554A patent/CA1338202C/fr not_active Expired - Fee Related
- 1989-02-06 EP EP19890301140 patent/EP0328333A3/fr not_active Withdrawn
- 1989-02-09 JP JP1030953A patent/JPH01252779A/ja active Pending
Patent Citations (4)
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US3594216A (en) * | 1969-06-19 | 1971-07-20 | Westinghouse Electric Corp | Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate |
US4485094A (en) * | 1983-01-28 | 1984-11-27 | Westinghouse Electric Corp. | Method of making ABO3 of the cubic perovskite structure |
EP0125638A2 (fr) * | 1983-05-13 | 1984-11-21 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Film précurseur pour film céramique, son utilisation et son procédé de préparation |
DE3827069A1 (de) * | 1987-11-21 | 1989-06-08 | Asea Brown Boveri | Verfahren zur herstellung eines supraleiters |
Non-Patent Citations (5)
Title |
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APPLIED PHYSICS LETTERS vol. 53, no. 18, 31 October 1988, pages 1750-1752, New York, US; J. ZHAO et al.: "Organometallic chemical vapor deposition of high Tc superconducting films using a volatile, fluorcarbon-based precursor" * |
APPLIED PHYSICS LETTERS vol. 53, no. 18, 31 October 1988, pages 1756-1758, New York, US; A.J. PANSON et al.: "Chemical vapor deposition of YBa2Cu307 using metalorganic chelate precursors" * |
IEEE TRANSACTIONS ON MAGNETICS vol. MAG-23, no. 2, March 1987, pages 999-1002; E.J. CUKAUSAS et al.: "Metal Organic Chemical Vapor Deposition of the Niobium-Nitrogen-Carbon System" * |
JAPANESE JOURNAL OF APPLIED PHYSICS vol. 27, no. 1, January 1988, pages L73-L76; M. FUTAMOTO et al.: "Preparation of YBa2Cu307-gamma Thin Films by Heat-Oxidation of Vacuum-Deposited Multilazer Metallic Films" * |
PHYSICAL REVIEW LETTERS vol. 58, no. 24, 15 June 1987, pages 2579-2581; S.R. OVSHINSKY et al.: "Superconductivity at 155 K" * |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0329103A2 (fr) * | 1988-02-17 | 1989-08-23 | Kabushiki Kaisha Riken | Procédé pour la fabrication de couches minces d'oxyde supraconducteur à haute température critique |
EP0329103A3 (en) * | 1988-02-17 | 1990-10-10 | Kabushiki Kaisha Riken | Process for manufacturing thin film of high-tc superconducting oxide |
US5284824A (en) * | 1988-03-16 | 1994-02-08 | Kabushiki Kaisha Toshiba | Method for manufacturing an oxide superconductor thin film |
US5204314A (en) | 1990-07-06 | 1993-04-20 | Advanced Technology Materials, Inc. | Method for delivering an involatile reagent in vapor form to a CVD reactor |
US5225561A (en) * | 1990-07-06 | 1993-07-06 | Advanced Technology Materials, Inc. | Source reagent compounds for MOCVD of refractory films containing group IIA elements |
US5280012A (en) * | 1990-07-06 | 1994-01-18 | Advanced Technology Materials Inc. | Method of forming a superconducting oxide layer by MOCVD |
US5453494A (en) * | 1990-07-06 | 1995-09-26 | Advanced Technology Materials, Inc. | Metal complex source reagents for MOCVD |
US5711816A (en) * | 1990-07-06 | 1998-01-27 | Advanced Technolgy Materials, Inc. | Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same |
US8299286B2 (en) | 1990-07-06 | 2012-10-30 | Advanced Technology Materials, Inc. | Source reagent compositions and method for forming metal films on a substrate by chemical vapor deposition |
US6126996A (en) * | 1990-07-06 | 2000-10-03 | Advanced Technology Materials, Inc. | Metal complex source reagents for chemical vapor deposition |
US5998236A (en) * | 1996-11-27 | 1999-12-07 | Advanced Technology Materials, Inc. | Process for controlled orientation of ferroelectric layers |
US5876503A (en) * | 1996-11-27 | 1999-03-02 | Advanced Technology Materials, Inc. | Multiple vaporizer reagent supply system for chemical vapor deposition utilizing dissimilar precursor compositions |
US5719417A (en) * | 1996-11-27 | 1998-02-17 | Advanced Technology Materials, Inc. | Ferroelectric integrated circuit structure |
US5882416A (en) * | 1997-06-19 | 1999-03-16 | Advanced Technology Materials, Inc. | Liquid delivery system, heater apparatus for liquid delivery system, and vaporizer |
US5923970A (en) * | 1997-11-20 | 1999-07-13 | Advanced Technology Materials, Inc. | Method of fabricating a ferrolelectric capacitor with a graded barrier layer structure |
US6284654B1 (en) | 1998-04-16 | 2001-09-04 | Advanced Technology Materials, Inc. | Chemical vapor deposition process for fabrication of hybrid electrodes |
US6821891B2 (en) | 2001-11-16 | 2004-11-23 | Applied Materials, Inc. | Atomic layer deposition of copper using a reducing gas and non-fluorinated copper precursors |
WO2003044242A3 (fr) * | 2001-11-16 | 2003-09-18 | Applied Materials Inc | Depot de couche atomique de cuivre au moyen d'un gaz de reduction et de precurseurs de cuivre non fluores |
WO2003044242A2 (fr) * | 2001-11-16 | 2003-05-30 | Applied Materials, Inc. | Depot de couche atomique de cuivre au moyen d'un gaz de reduction et de precurseurs de cuivre non fluores |
EP1564489A1 (fr) | 2004-02-10 | 2005-08-17 | General Electric Company | Bougie d'allumage de chambre de combustion de turbine à gaz |
US9112106B2 (en) | 2004-03-11 | 2015-08-18 | Nexans | Precursor composition for YBCO-based superconductors |
EP1655788A2 (fr) * | 2004-11-03 | 2006-05-10 | Nexans | Précurseur pour supraconducteurs à base de YBCO |
EP1655787A1 (fr) * | 2004-11-03 | 2006-05-10 | Nexans | Composition de précurseur pour supraconducteur à base de YBCO |
EP1655788A3 (fr) * | 2004-11-03 | 2007-02-14 | Nexans | Précurseur pour supraconducteurs à base de YBCO |
Also Published As
Publication number | Publication date |
---|---|
EP0328333A3 (fr) | 1990-12-27 |
CA1338202C (fr) | 1996-04-02 |
JPH01252779A (ja) | 1989-10-09 |
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